CN102539548A - Method and device for purifying dioxin substance in environmental matrix extracting solution by using one-stage method - Google Patents
Method and device for purifying dioxin substance in environmental matrix extracting solution by using one-stage method Download PDFInfo
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- CN102539548A CN102539548A CN2011103966852A CN201110396685A CN102539548A CN 102539548 A CN102539548 A CN 102539548A CN 2011103966852 A CN2011103966852 A CN 2011103966852A CN 201110396685 A CN201110396685 A CN 201110396685A CN 102539548 A CN102539548 A CN 102539548A
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Abstract
The invention discloses a method and device for purifying a dioxin substance in an environmental matrix extracting solution by using a one-stage method. The method comprises decontamination steps of: preparing a composite chromatographic column, prewashing the composite chromatographic column by using normal hexane, adding the environmental matrix extracting solution in the composite chromatographic column, eluting impurities by using the normal hexane and a normal hexane/dichloromethane mixed solution in sequence, and then, eluting the dioxin substance by using a dichloromethane solution. Filling materials of the composite chromatographic column comprise silanizing glass wool, quartz sand, florisil magnesium silicate, deactivating alkaline aluminum oxide, a neutral silica gel, an alkaline silica gel, the neutral silica gel, an acidic silica gel and anhydrous sodium sulfate in sequence from bottom to top. Compared with the prior art, the method and the device has the advantages that: the time of purification treatment can be shortened while the decontamination effect is guaranteed; the decontamination efficiency is improved; the dosage of an eluting solvent is reduced; and the cost is saved.
Description
Technical field
The present invention relates to the environment measuring technical field, be specifically related to the method and the device of dioxin-like chemical in a kind of purifying environmental matrices extract.
Background technology
Dioxin is claimed the dioxa glutinous rehmannia again, is a kind of colorless and odorless, liposoluble substance that toxicity is serious, and is serious to human harm.Dioxin is actually abbreviation of dioxin; What it referred to is not a kind of one matter; But structure totally 210 kind the two big type organic compounds that comprise numerous congeners or isomeride all very similar with character, promptly polychlorinated dibenzo-2 is disliked English (PCDDs) and polychlorinated dibenzo (PCDFs).
The analysis of dioxin belongs to ultratrace, multicomponent analysis in the environment, and matrix effect is complicated, and qualitative and quantitative detection is complicated, and it is key link that complete purification process detects for organic micro-pollutant.In the development of purification process, mainly be at present to filler selection and robotization and systematized improvement.At present; The purification method of carrying out has the five step methods of purification of promoting in International Standards Method, national standard method and the industry; Wherein, Five commonly used step purification methods are thorough to sample purification, flow process simple, can accurately measure the content of dioxin and polychlorinated biphenyl, and returning to contract etc. for environmental evaluation, risk assessment and research pollutant source provides reliable experimental technique guarantee.This method comprises that acidic silica gel column purification, multistage silicagel column purify, gel permeation chromatographic column purifies, five purifying step of alkali alumina column purification Fu Luoli magnesium silicate column purification; But have following shortcoming: whole purification process is long; Step is more loaded down with trivial details; The time that needs is longer, and purification method is complicated,, having relatively high expectations to laboratory condition high to analyst's requirement.Above issues limit carrying out fast of dioxin testing.
Summary of the invention
The object of the present invention is to provide the method for dioxin-like chemical in a kind of purifying environmental matrices extract, this method is quick, stable, simple and easy, cheap, can extensively apply to common organic analysis laboratory, promotes carrying out fast of dioxin testing.
Technical scheme of the present invention is:
Utilize the sulfurization of sulfuric acid, acidic silica gel is placed the upper strata, remove most matrix effect earlier; Help the purification of lower post chromatography; And between the alkaline silica gel, it is separated to add one deck neutral silica gel work pad, influences purification effect with the neutralization reaction of avoiding Acidity of Aikalinity silica gel.The highly active Fu Luoli magnesium silicate of lower floor can separate dioxin (PCDD/Fs) and polychlorinated biphenyl (PCBs) preferably; Though take off alkali alumina alive is requisite filler in dioxin (PCDD/Fs) the purification process process; But can not remove the interference of part polychlorinated biphenyl (PCBs); Based on this alkali alumina is taken off the top of living and placing the Fu Luoli magnesium silicate, make it remove the low pole material earlier, realize again and the separating of polychlorinated biphenyl (PCBs).
The method of dioxin-like chemical in the one-stage process purifying environmental matrices extract of the present invention comprises following purifying step:
1) preparation of composite chromatography post: get the full glass chromatography column that the bottom has tetrafluoro joint door, from bottom to top insert silanized glass cotton, silica sand, Fu Luoli magnesium silicate successively, take off alkali alumina alive, neutral silica gel, alkaline silica gel, neutral silica gel, acidic silica gel and anhydrous sodium sulfate;
2) wash the composite chromatography post with the normal hexane pre-leaching;
3) in compound chromatographic column, add the environmental matrices extract, with normal hexane wash-out impurity;
4) with normal hexane/methylene chloride mixed solution drip washing, wash-out contains the sample solution of polychlorinated biphenyl and other components;
5) use dichloromethane solution drip washing, obtain containing the sample solution of dioxin-like chemical.
Behind the composite chromatography post that extract adding pre-leaching was washed; Acid, alkaline silica gel section can be removed most of matrix interference such as phenols in the matrix, acidic materials, lipid, protein, sulfide, aliphatic hydrocarbon compounds and residual strong polar material, pigment, polynuclear aromatics; Take off alkali alumina section alive and can remove low pole material, organochlorine compound and grease class etc.; Dioxin (PCDD/Fs) and polychlorinated biphenyl (PCBs) mainly are adsorbed on Fu Luoli magnesium silicate layer; Add the normal hexane eluent, wash-out low pole material, organochlorine compound, grease class and most polychlorinated biphenyl etc.Improve the polarity of eluent; With the mixed solution of normal hexane/methylene chloride (95: 5; V: V) polychlorinated biphenyl (PCBs) chaff interference is washed off, with the stronger dichloromethane solution of polarity dioxin (PCDD/Fs) component is eluted at last, to reach the effect of abundant purifying PCDD/Fs.
Preferably, the volume ratio of normal hexane and methylene chloride is 95: 5 in normal hexane/methylene chloride mixed solution.
Preferably, the filler in the full glass chromatography column passes through following processing before use:
Neutral silica gel: with muffle furnace under 550 ℃ of conditions, dewater deactivate be placed on more than the 12h in the exsiccator preserve subsequent use;
Acidic silica gel: the mass ratio of silica gel and sulfuric acid is 6: 4, promptly in flask, takes by weighing the 60g activated silica gel, adds the 40g concentrated sulphuric acid, and jumping a queue vibrates to silica gel becomes even flow state;
Alkaline silica gel: the mass ratio of silica gel and sodium hydroxide solution is 67: 33, and in the 67g activated silica gel, adding 33g concentration is the sodium hydroxide solution of 1mol/L, shakes up, subsequent use;
Take off alkali alumina alive: alkali alumina is placed 500 ℃ of muffle furnace activation 8 hours, after go to and reduce to room temperature in the exsiccator, get in the alkali alumina of 97g activation and add the 3g high purity water, shake up, subsequent use;
The Fu Luoli magnesium silicate: use preceding 550 ℃ of activation 12h, place exsiccator to reduce to room temperature, sealing is preserved;
Anhydrous sodium sulfate is used for before the use being cooled to room temperature more than 450 ℃ of roasting 4h, is contained in to place the interior preservation of exsiccator subsequent use in the port grinding bottle;
Glass wool and silica sand: 450 ℃ of roastings are subsequent use more than 4 hours;
Cotton and filter paper: with after methylene chloride ultrasonic half an hour three times, after vacuum is drained solvent, place preserve in the exsiccator subsequent use.
Another object of the present invention provides a kind of device that is used for purifying environmental matrices extract dioxin-like chemical; This device comprises that the bottom has the full glass chromatography column of tetrafluoro joint door, and the filler in the said full glass chromatography column from bottom to top is followed successively by silanized glass cotton, silica sand, Fu Luoli magnesium silicate, takes off alkali alumina alive, neutral silica gel, alkaline silica gel, neutral silica gel, acidic silica gel and anhydrous sodium sulfate.
Preferably, the complete long 25cm of glass chromatography column, the cotton high 1cm of filler silanized glass, the high 1cm of silica sand, Fu Luoli magnesium silicate 1g takes off alkali alumina 3g alive, neutral silica gel 3g, alkaline silica gel 4g, neutral silica gel 3g, acidic silica gel 40g, the high 1cm of anhydrous sodium sulfate.
Compared with prior art, the beneficial effect that the present invention produces is: the eluting solvent of oversimplifying purifying step, using when saving clarification time and purification, improved purification efficiency greatly.
Embodiment
Through the practical implementation example the present invention has been done further explain below and understood the technical scheme that the present invention protects so that know.
Embodiment 1
1) preparation of material:
1. neutral silica gel: 70～230 orders, it is subsequent use to be placed in the exsiccator preservation with 550 ℃ of activation 12h of muffle furnace before using;
2. acidic silica gel (40%H
2SO
4): in flask, take by weighing the 60g activated silica gel, add the pure concentrated sulphuric acid of 40g top grade, jumping a queue vibrates to silica gel becomes even flow state;
3. alkaline silica gel (33%): in the 67g activated silica gel, adding 33g concentration is the sodium hydroxide solution of 1mol/L, shakes up, subsequent use;
4. take off alkali alumina (3%H alive
2O): with 500 ℃ of muffle furnace activation 8 hours, place exsiccator to reduce to room temperature the high-purity alkali alumina of 150 purposes, add the 3g high purity water in the alkali alumina after the 97g activation, shake up, subsequent use;
5. Fu Luoli magnesium silicate: 60～100 orders, 550 ℃ of activation 12h place exsiccator to reduce to room temperature, and sealing is preserved;
6. anhydrous sodium sulfate: top grade is pure, is used for being cooled to room temperature more than 450 ℃ of roasting 4h, be contained in place in the port grinding bottle preserve in the exsiccator subsequent use;
7. glass wool and silica sand: 450 ℃ of roastings are subsequent use more than 4 hours;
8. cotton and filter paper: with after methylene chloride ultrasonic half an hour three times, after vacuum is drained solvent, place preserve in the exsiccator subsequent use.
2) purification devices: select internal diameter 2.5cm for use, the normal pressure of column length 25cm bottom band tetrafluoro joint door is pressed glass chromatography column, and is cotton by inserting the high silanized glass of 1cm on following the reaching successively; The high silica sand of 1cm; 1g Fu Luoli magnesium silicate, 3g takes off alkali alumina alive, 3g neutral silica gel, 4g alkaline silica gel, 3g neutral silica gel, 40g acidic silica gel; The high 1cm of anhydrous sodium sulfate processes the composite chromatography post.
3) purification process: wash the composite chromatography post with the pre-leaching of 80ml normal hexane earlier, in compound chromatographic column, add the environmental matrices extract again, with 120ml normal hexane wash-out impurity; The solution that obtains discards; Use 30ml volume ratio is normal hexane/methylene chloride mixed solution drip washing of 95: 5, and wash-out contains the sample solution of polychlorinated biphenyl and other components, and this part solution discards; Use the drip washing of 100ml dichloromethane solution at last, obtain containing the sample solution of dioxin-like chemical.
Embodiment 2
Embodiment 2 methods of the present invention and existing five contrasts of step purification method on solvent and time consumption
Prepare 12 identical environmental matrices extract samples; 6 existing methods of samples using purify; Promptly carry out acidic silica gel column purification, the purification of multistage silicagel column, gel permeation chromatographic column purification, five step of alkali alumina column purification Fu Luoli magnesium silicate column purification purification process successively; Record purifies employed quantity of solvent and clarification time, and results averaged is as shown in table 1; 6 samples using methods of the present invention purify, and record purifies employed quantity of solvent and clarification time, and results averaged is as shown in table 1; The model of using U.S. Waters company to produce is at last steamed concentrate as standardization in height explanation gas chromatography/high-resolution double focusing GC-MS utilization isotope of HP6890N GC/Autospec Premierr to revolving of 12 samples after purifying and is detected, the value basically identical of the FCDD/Fs in 12 samples.
The existing five step method of purification and the contrasts of the inventive method on solvent and time consumption of table 1
Can know that by table 1 contrast method of the present invention can reduce to 7 hours by 24 hours with the clarification time, purification efficiency has promoted 71%, two kind of purifying solvent use amount and has reduced 464.5ml and 70.5ml respectively, has saved 67% and 41% respectively.
Above-mentioned embodiment is merely preferred implementation of the present invention, can not limit protection scope of the present invention with this, and the variation of any unsubstantiality that those skilled in the art is done on the basis of invention and replacement all belong to the present invention's scope required for protection.
Claims (5)
1. the method for dioxin-like chemical in the one-stage process purifying environmental matrices extract comprises following purifying step:
1) preparation of composite chromatography post: get the full glass chromatography column that the bottom has tetrafluoro joint door, from bottom to top insert silanized glass cotton, silica sand, Fu Luoli magnesium silicate successively, take off alkali alumina alive, neutral silica gel, alkaline silica gel, neutral silica gel, acidic silica gel and anhydrous sodium sulfate;
2) wash the composite chromatography post with the normal hexane pre-leaching;
3) in compound chromatographic column, add the environmental matrices extract, with normal hexane wash-out impurity;
4) with normal hexane/methylene chloride mixed solution wash-out;
5) use dichloromethane solution drip washing, obtain containing the sample solution of dioxin-like chemical.
2. the method for claim 1, it is characterized in that: the volume ratio of normal hexane and methylene chloride is 95:5 in normal hexane/methylene chloride mixed solution.
3. the method for claim 1 is characterized in that: the filler in the full glass chromatography column passes through following processing before use:
Neutral silica gel: with muffle furnace under 550 ℃ of conditions, dewater deactivate be placed on more than the 12h in the exsiccator preserve subsequent use;
Acidic silica gel: the mass ratio of silica gel and sulfuric acid is 6:4, promptly in flask, takes by weighing the 60g activated silica gel, adds the 40g concentrated sulphuric acid, and jumping a queue vibrates to silica gel becomes even flow state;
Alkaline silica gel: the mass ratio of silica gel and sodium hydroxide solution is 67:33, and in the 67g activated silica gel, adding 33g concentration is the sodium hydroxide solution of 1mol/L, shakes up, subsequent use;
Take off alkali alumina alive: alkali alumina is placed 500 ℃ of muffle furnace activation 8 hours, after go to and reduce to room temperature in the exsiccator, get in the alkali alumina of 97g activation and add the 3g high purity water, shake up, subsequent use;
The Fu Luoli magnesium silicate: use preceding 550 ℃ of activation 12h, place exsiccator to reduce to room temperature, sealing is preserved;
Anhydrous sodium sulfate is used for before the use being cooled to room temperature more than 450 ℃ of roasting 4h, is contained in to place the interior preservation of exsiccator subsequent use in the port grinding bottle;
Glass wool and silica sand: 450 ℃ of roastings are subsequent use more than 4 hours;
Cotton and filter paper: with after methylene chloride ultrasonic half an hour three times, after vacuum is drained solvent, place preserve in the exsiccator subsequent use.
4. device that is used for purifying environmental matrices extract dioxin-like chemical; Comprise that the bottom has the full glass chromatography column of tetrafluoro joint door, it is characterized in that: the filler in the said full glass chromatography column from bottom to top is followed successively by silanized glass cotton, silica sand, Fu Luoli magnesium silicate, takes off alkali alumina alive, neutral silica gel, alkaline silica gel, neutral silica gel, acidic silica gel and anhydrous sodium sulfate.
5. device as claimed in claim 4; It is characterized in that: the complete long 25cm of glass chromatography column, the cotton high 1cm of filler silanized glass, the high 1cm of silica sand; Fu Luoli magnesium silicate 1g; Take off alkali alumina 3g alive, neutral silica gel 3g, alkaline silica gel 4g, neutral silica gel 3g, acidic silica gel 40g, anhydrous sodium sulfate 1cm.
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| CN201110396685.2A CN102539548B (en) | 2011-12-02 | 2011-12-02 | Method and device for purifying dioxin substance in environmental matrix extracting solution by using one-stage method |
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| CN201110396685.2A CN102539548B (en) | 2011-12-02 | 2011-12-02 | Method and device for purifying dioxin substance in environmental matrix extracting solution by using one-stage method |
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Cited By (12)
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| CN104258596A (en) * | 2014-09-25 | 2015-01-07 | 上海市农业科学院 | Solid-phase extraction column for enriching and purifying deoxidized nivalenol |
| CN104487840A (en) * | 2013-05-27 | 2015-04-01 | 三浦工业株式会社 | Fractionation method for dioxins |
| CN105259013A (en) * | 2015-10-26 | 2016-01-20 | 哈尔滨工业大学 | Method for purifying bisphenol compound in surface water sample extraction liquid |
| CN105974001A (en) * | 2016-04-21 | 2016-09-28 | 广州普诺环境检测技术服务有限公司 | Method for pretreating soil or sediment sample and method for determining dioxin |
| CN109613130A (en) * | 2018-11-22 | 2019-04-12 | 环境保护部华南环境科学研究所 | Transfer dissolving method and liquid relief component based on bioanalysis detection dioxin sample |
| CN109633017A (en) * | 2018-12-29 | 2019-04-16 | 聂志强 | A kind of method and its detection method for extracting hexabromocyclododecane from landfill leachate |
| CN111089922A (en) * | 2019-12-31 | 2020-05-01 | 江苏微谱检测技术有限公司 | Sample purification method for gel permeation chromatography detection |
| CN112630337A (en) * | 2020-12-17 | 2021-04-09 | 生态环境部华南环境科学研究所 | Method for cooperatively detecting polychlorinated biphenyl and polybrominated diphenyl ether in soil |
| CN112666295A (en) * | 2020-12-30 | 2021-04-16 | 生态环境部华南环境科学研究所 | Method for extracting, cooperatively separating and detecting polychlorinated biphenyl and dioxin in soil |
| CN114887605A (en) * | 2022-04-24 | 2022-08-12 | 中国农业科学院油料作物研究所 | Perfluoro cotton solid phase extraction material and application thereof in enrichment and detection of organic fluoride |
| CN115963213A (en) * | 2023-02-08 | 2023-04-14 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in environmental medium |
| CN116908356A (en) * | 2023-07-19 | 2023-10-20 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Purifying device and method for brominated dioxin compounds in environmental sample |
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| CN104487840A (en) * | 2013-05-27 | 2015-04-01 | 三浦工业株式会社 | Fractionation method for dioxins |
| US9696290B2 (en) | 2013-05-27 | 2017-07-04 | Miura Co., Ltd. | Method for fractionating dioxins |
| CN104487840B (en) * | 2013-05-27 | 2017-09-12 | 三浦工业株式会社 | The fractionation method of dioxin |
| CN104258596A (en) * | 2014-09-25 | 2015-01-07 | 上海市农业科学院 | Solid-phase extraction column for enriching and purifying deoxidized nivalenol |
| CN105259013A (en) * | 2015-10-26 | 2016-01-20 | 哈尔滨工业大学 | Method for purifying bisphenol compound in surface water sample extraction liquid |
| CN105974001A (en) * | 2016-04-21 | 2016-09-28 | 广州普诺环境检测技术服务有限公司 | Method for pretreating soil or sediment sample and method for determining dioxin |
| CN109613130A (en) * | 2018-11-22 | 2019-04-12 | 环境保护部华南环境科学研究所 | Transfer dissolving method and liquid relief component based on bioanalysis detection dioxin sample |
| CN109633017A (en) * | 2018-12-29 | 2019-04-16 | 聂志强 | A kind of method and its detection method for extracting hexabromocyclododecane from landfill leachate |
| CN111089922A (en) * | 2019-12-31 | 2020-05-01 | 江苏微谱检测技术有限公司 | Sample purification method for gel permeation chromatography detection |
| CN112630337A (en) * | 2020-12-17 | 2021-04-09 | 生态环境部华南环境科学研究所 | Method for cooperatively detecting polychlorinated biphenyl and polybrominated diphenyl ether in soil |
| CN112666295A (en) * | 2020-12-30 | 2021-04-16 | 生态环境部华南环境科学研究所 | Method for extracting, cooperatively separating and detecting polychlorinated biphenyl and dioxin in soil |
| CN114887605A (en) * | 2022-04-24 | 2022-08-12 | 中国农业科学院油料作物研究所 | Perfluoro cotton solid phase extraction material and application thereof in enrichment and detection of organic fluoride |
| CN114887605B (en) * | 2022-04-24 | 2023-10-03 | 中国农业科学院油料作物研究所 | Perfluoro cotton solid phase extraction material and application thereof in enrichment and detection of organic fluoride |
| CN115963213A (en) * | 2023-02-08 | 2023-04-14 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in environmental medium |
| CN116908356A (en) * | 2023-07-19 | 2023-10-20 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Purifying device and method for brominated dioxin compounds in environmental sample |
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